Gold(I)‐Catalyzed Cycloisomerization of 1,6‐Diynes: Synthesis of 2,3‐Disubstituted 3‐Pyrroline Derivatives

Abstract

Ein neuartiger Zugang zu den Titelverbindungen nutzt die goldkatalysierte Cycloisomerisierung von 1,6‐Diinen, die eine Propargylester‐ und eine Aren‐In‐Einheit enthalten. Die fünfgliedrigen Stickstoffheterocyclen wurden in akzeptablen bis guten Ausbeuten erhalten (siehe Schema; Tf=Triflat). Aus Deuterium‐Markierungsexperimenten wurde ein wahrscheinlicher Reaktionsmechanismus abgeleitet.

In Situ Generation of Nucleophilic Allenes by the Gold‐Catalyzed Rearrangement of Propargylic Esters for the Highly Diastereoselective Formation of Intermolecular C(sp3)C(sp2) Bonds

“…In the last few years, in the field of homogeneous gold catalysis [1] rearrangement reactions involving propargylic esters have received considerable attention owing to the synthetic utility of these easily accessible compounds in a wide variety of intriguing, fascinating transformations. [2] It is established that in gold catalysis these propargylic esters can undergo 1,2-or 1,3-acyloxy migration leading to a gold vinyl carbenoid species or a gold allenic intermediate (Scheme 1), [3] which can be further trapped by other functional groups to allow the synthesis of diverse organic products. The gold vinyl carbenoid species can undergo prototypical reactions, for example the cyclopropanation of alkenes and dienes, as well as insertion into CÀH bonds.…”

Gold-catalyzed cycloisomerization strategies for the stereoselective synthesis of carbocycles from alkynes

“…Yield 85%; yellow oil; 1 15.5, 44.2, 73.1, 81.0, 90.3, 91.5, 106.9, 114.4, 123.2, 125.5, 126.1, 128.0, 128.4, 131.8, 136.4, 136.9, 143.9; IR (NaCl, neat) v: 3439, 3018, 2961, 2168, 1601, 1246 cm -1 ; HRMS (ESI) calcd. for C 24 H 25 Si (M + H): 341.1726, found: 341.1727.…”

“…In 2011, Shi and co-workers reported the first example in which gold-catalyzed cycloisomerization of internal 1,6-diyne esters 80 connected by a nitrogen atom gave nitrogen-containing five-membered heterocyclic rings 87 in 35-88% yield (Scheme 1.18). 24 In this work, it was proposed that this reaction was likely to proceed via two possible pathways. In pathway a, 1,6-diyne ester 80 was activated by gold catalyst to…”

“…Yield 91%; colorless oil; 1 4, 43.7, 76.2, 77.6, 78.4, 81.0, 88.5, 122.7, 125.2, 127.9, 128.3, 128.5, 128.6, 129.8, 130.0, 130.3, 133.3, 140.4, 164.0;IR (NaCl, neat) v: 3287, 3019, 2120, 1734, 1273 ; HRMS (ESI) calcd. for C 24 8,44.0,77.7,78.5,79.1,81.0,93.9,121.4,125.2,125.3,126.3,126.3,126.6,128.2,128.3,128.5,128.7,129.8,130.2,130.3,133.2,133.3,133.5,140.5,164.0;IR (NaCl,neat) 7-(phenanthren-9-yl)-3-phenylhepta-1,6-diyn-3-yl benzoate (106r 15.8, 43.9, 77.7, 78.5, 79.3, 81.0, 93.6, 120.1, 122.6, 122.8, 125.2, 126.9, 127.0, 127.0, 127.3, 128.4, 128.5, 128.7, 129.9, 130.1, 130.1, 130.3, 131.3, 131.4, 131.5, 133.3, 140.5, 164.1;IR (NaCl, neat) v: 3302, 3019, 2278, 1734, 1450 7-(cyclohex-1-en-1-yl)-3-phenylhepta-1,6-diyn-3-yl 3-methoxybenzoate (106s 6, 22.4, 25.6, 29.5, 44.0, 55.4, 77.5, 78.5, 80.9, 82.8, 85.8, 114.3, 119.7, 120.8, 122.1, 125.1, 128.2, 128.5, 129.5, 131.6, 133.7, 140.4, 159.6, 163.9;IR (NaCl, neat) v: 3302, 3019, 2940, 2120, 1728, 1273, 1215 cm -1 ; HRMS (ESI) calcd. for C 27…”

“…for C 23 3-cyclopropyl-7-(4-methoxyphenyl)hepta-1,6-diyn-3-yl benzoate (106x 3.6, 15.1, 17.9, 39.7, 55.2, 75.9, 79.1, 80.6, 80.9, 87.6, 113.8, 115.9, 128.4, 129.7, 130.9, 132.9, 132.9, 159.1, 164.6;IR (NaCl, neat) v: 3302, 3019, 2120, 1722, 1527, 1215 ; HRMS (ESI) calcd. for C 24 31.1, 31.5, 55.3, 78.1, 78.4, 81.2, 82.2, 97.4, 124.2, 125.3, 127.5, 128.0, 128.1, 128.4, 128.5, 129.9, 130.6, 131.6, 133.0, 142.2, 164.2;IR (NaCl, neat) v: 3300, 3019, 2120, 1730, 1273, 1215 ; HRMS (ESI) calcd. for C 28 H 25 O 2 (M + +H): 393.1855, found: 393.1859.…”